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By Jyri Talja, Shaolong Chen, Hannu Mansikkaviita

"Drying (water removal) prior to smelting is always economically feasible. Unnecessary heating of vapour can thus be eliminated resulting in savings of5-15 MUSD every year.Thermodynamically removal of one ton of water out of copper concentrate at 100 °C (with 10 % moisture) requires approximately 3150 MJ/tH2o, consisting of heating of the water (377 MJ), heating of the concentrate (509 MJ) and water evaporation (2260 MJ). This is quite independent of the selected drying technology. In reality some more heat is needed as higher temperature is practiced to enhance the drying performance and to reduce the equipment size.Major nominator in drying energy efficiency is amount of gases, which depends greatly on the drying technology. Dryers based on direct heating with fossil fuels have high gas flow rates, and thus they require additional energy of about 1400-1600 MJ/tH2o, compared to indirect modemsteam drying at 250-400 MJ/tH2o.Significant benefits in energy consumption (900-1300 MJ/tH2o) with additional potential for a bonus profit of 2-4 MUSD/y year, together with full elimination of some 40 000 tpy CO2 per mid-size dryer is available by selecting sustainable, energy efficient steam drying.IntroductionRemoval of water from the concentrate is very energy intensive thus having a significant environmental impact. However, drying prior to smelting is always economically feasible and very often viable also from the perspective of process operations. This environmental impact of drying can, however, be decreased or even fully eliminated with proper selection of the drying technology.Energy incorporated in drying consists always of a number of phases like liquid (water), solids (concentrate) and gases (water vapour, purging I dilution air, combustion gases). Each phase is heated to a specific temperature during the drying process.Heating of water, heating of the concentrate and water evaporation consumes more or less the same amount of energy despite of the drying technology (3150 MJ per ton of water). In conventional drying this amount of energy is achieved by combustion of fossil fuels wirg subsequent CO2 emission. Alternatively, chemical energy derived from sulphide smelting can be utilized in a form of steam thus generating zero emission ofCO2, in modem steam drying."

Jan 1, 2012

By Horace R. Graham

CHEMICAL nitrogen and the "nitrates" of commercial significance are derived mainly from three basic sources: (1) the natural deposits in the form of nitrate-bearing earth and clay, which, being largely water-soluble, can exist only in the most arid portions of the earth; (2) coal, which yields not only nitrogen but also the additional by-product hydrogen required for the synthesis of ammonia and its compounds; (3) the atmospheric air, which contains 75.5 pct by weight of pure nitrogen gas. NATURAL NITRATE DEPOSITS Occurrence Although natural nitrate deposits consisting principally of the salts of sodium and potassium have been reported in Egypt, South Africa, Mexico, Argentina, Colombia, Peru and the USA, the only known natural nitrate resources of commercial importance are the vast deposits found in the Atacama, Tarapaca and Antofagasta regions of northern Chile, lying in a narrow strip 10 to 50 miles wide and roughly 450 miles long, between latitudes [19O] and [26OS]. In addition to yielding nitrates of sodium and potassium, these deposits are the source of the major portion of the world's supply of iodine. The nitrate-bearing ores known in Chile as caliche are variable in composition and may contain from 5 to 30 pct each of nitrate, chloride and sulphate. While the deposits are present chiefly in the form of the sodium salt, potassium, magnesium and calcium also occur in percent- ages from 0.1 to 5; usually as double salts with sulphate, which are but slightly soluble in nitrate leach solutions. These double salts are bloedite(Na2S04.MgS04.4H,0), glauberite (Na2S04.CaS04), polyhalite (K2SO4.- MgS04.2CaS04.2H20). Some deposits contain up to30 pct of their ni-

Jan 1, 1949

By L. A. Haas

S02 reduction with CO was studied in an integral flow reactor at a nominal flow of 0.5 liter per minute. Reactant gas contained 3 percent SO2, 6 percent CO, and the balance He. SO2 conversion was determined for three different types of catalysts. The first consisted of 16 commercial catalysts used for various chemical syntheses. Only the commercial catalysts which contained transition metals in alumina removed more than 30 percent 80a at temperatures below 510° C. Two other types of catalysts were prepared in the laboratory either by pelletizing equal amounts of powdered alumina and transition metal oxides or by impregnating commercial alumina tablets with transition metal ions. Regardless of preparation techniques, Cr and Fe in alumina were the two best catalysts. The observed results suggest that an intermediate (SCO) is formed by the interaction of surface metal sulfides and carbonyls. Alumina then catalyzes the interaction of SCO with S02 to form the end products (sulfur and carbon dioxide). Over 80 percent S02 was removed at 460° C with 2 grams alumina impregnated with 2.5 percent iron.

Jan 1, 1972

By Warren D. Stanford Stanford

Introduction The Sleeper mine is a near-surface gold mine located in a remote area 56 km (35 air miles) northwest of Winnemucca, NV (Fig. 1). The deposit was discovered in 1984 by an Amax exploration geologist. Favorable drilling results led to feasibility studies and metallurgical testwork. Final evaluation of the mine potential proceeded very quickly. The project received Amax board approval in July 1985. Eight months later, the process plant was fully operational. The first gold ($1 million) was shipped one month later, in March 1986. Total plant capital was $27 million. Payback was achieved in six months. The Sleeper mine was expected to produce 1.6 t (53,000 oz) of gold and 1.3 t (41,000 oz) of silver annually. However, the ore body exceeded all expectations. Production for the first 10 months of operation amounted to 4 t (128,000 oz) of gold and 2.9 t (94,000 oz) of silver. Direct cash operating costs are in the $1.77/g ($55 per oz) range. Amax is actively conducting exploration nearby for additional reserves to extend the mine's life. (See update on page 242.) Geology The Sleeper gold deposit is located on the northwestern flank of the Slumbering Hills and in the Awakening Mining District. Rocks exposed in the vicinity of the deposit are interbedded siltstones, sandstones, and limestones of Triassic age. They are overlain by latite lava flows and tuffs of Tertiary age. Dikes and sills of latite and andesite intrude the sedimentary rocks. Quaternary deposits of mostly sand with minor gravel and clay cover a pediment containing the gold deposit. The sedimentary and volcanic rock units have been transsected and offset by extensive north- northeast trending faults and less abundant northwest trending faults. Both fault systems fractured and prepared the ground for subsequent invasions of mineral-bearing hot spring geothermal waters. The hot spring systems produced widespread hydrothermal alteration and gold mineralization at silicified centers near feeder fault structures. The deposit is hosted by siltstone and latite that have been hydrothermally brecciated. The main breccia is elongated north-northeasterly. The hydrothermal breccia zones appear to dip steeply to the west. Gold mineralization consists of native gold and electrum deposited in two or more high-grade quartz-breccia veins. Lower grade gold mineralization occurs

Jan 4, 1987

By Robert Hopler

In the annual report under the Explosives Act for 1905, H.M.inspectors state that over 90 percent of the accidents causing death or personal injury occurred in the use of explosives and under miscellaneous conditions to which the controlling provisions of the Act do not apply, and that such accidents caused 43 out of the 50 deaths, and 312 out of 348 cases of injury. The number of accidents grouped under the heading of “Use and Miscellaneous” is less than that for 1904 - viz., 281 against 301. By these accidents 43 persons were killed and 312 injured, as compared with 39 killed and 343 injured in 1904

Jan 1, 2007

By G. L. Boxer, R. A. Metz, C. B. Smith, W. J. Atkinson

Since the inception of the Ashton (formerly Kalumburu) Joint Venture in 1972 the parties have expended $24 million in exploration for diamonds in the Kimberley region. This has resulted in the discovery of the currently subeconomic Ellendale deposits in 1976/77 and the economic Argyle - Smoke Creek Deposits in 1979/80. In addition to Argyle and Ellendale, some 90 kimberlitic and lamproitic bodies have been discovered grouped broadly into three provinces, on the west, east and north margins of the Kimberley block. These bodies range in size from dyke-like features less than 1. m (3 ft) in width to pipes with a surface area of 128 ha (316 acres). The bodies with larger surface area are volcanic crater deposits, infilled with air-fall and water deposited tuffs and epiclastic sediments. Diamond content ranges from trace to economic concentrations. The exploration discoveries were facilitated by early recognition that the petrography, mineralogy and chemistry of the diatremes varied from the classical kimberlites of Kimberley, South Africa, to unusual more highly fractionated, alkaline, silicic varieties having affinities with leucitelamproite. Indirect methods of exploration were used, primary reconnaissance work being stream gravel sampling for kimberlitic indicator minerals. Evaluation showed Ellendale diamonds are 90% gem and near gem, but the low grades and tonnage render the deposits unpayable at today's diamond prices. After discovery in late 1979 and completion of a feasibility study by the end of 1982, evaluation studies proved Argyle to be economic. Alluvial diamond mining commenced in 1983 producing 6.2 million carats (Mct) that year, 60% being of industrial quality. Open-pit mining of the AK1 lamproite should start in 1985/1986 at a rate of 3 million t/a (33 million stpy) and produce 25 Mct/a, making this mine, and Australia, the world's largest producer of diamonds by weight. The revenue from diamond deposits is a function of the grade and the value of the diamonds. The grade is the product of the frequency of occurrence of the diamonds (stone density) and the mean stone size; the value of the stones is strongly related to their size distribution. During evaluation of the West Australian deposits, the diamond distribution was found to vary markedly in stone density and stone size. These variations corresponded with changes in the rock type hosting the mineralization. As a consequence, geological mapping of individual lamproites within the multiple vents and careful monitoring of the diamond distribution became an important part of the evaluation work. Similar variations in stone size and frequency were found to accord with separate alluvial terraces and fan gravels derived by erosion from the Argyle AM lamproite.

Jan 1, 1992

By P. A. Hendricks

The surface coal mining industry in the United States employs over 50,000 people and is responsible for 60% of domestic coal production. This represents a very significant contribution to our national economy and an important source of highly skilled and well paying jobs. The U.S. Bureau of Mines (USBM) has targeted surface mining as an important research priority to reduce the social and economic costs associated with surface mining injuries and fatalities. USBM safety research focuses on the development of technologies that can enhance productivity and reduce mining costs through a reduction in the number and severity of mining accidents. This report summarizes a number of completed and ongoing research programs that address a broad range of surface mining safety problems. Research methods are described, and research products which are suitable for industry implementation are highlighted.

Jan 1, 1994

By R Robinson

Modem occupational health practice can be described as the fitting of work to the individual and each individual to his job; perhaps a non-traditional way to view occupational health. This two-component description is achieved through the development of programs to implement and monitor specific job procedures, from the monitoring of unwanted exposures to contaminants to the auditing of mine sites. This paper is about such programs. Some attempt must be made to evaluate the effectiveness of the program and several performance indicators which are intended to measure the effectiveness of such a program are offered.

Jan 1, 1994

By F. J. Plecity, J. T. Michalak, W. C. Leslie

W. M. Williams (McGill University)-The authors are to be congratulated on completing this detailed investigation of recrystallization behavior. The present writer has recently completed some research at the University of Toronto on the recrystallization and grain growth behavior of a number of "pure" irons, and he would like to take issue with the authors' contention that recrystallization cannot be followed by means of hardness measurements. Two series of specimens of Ferrovac E, a com- mercially available iron, were annealed to complete recrystallization at 525" and 620" C, measurements being made both of Rockwell hardness and of volume percent recrystallized as a function of annealing time. Good correlation was found between these two quantities and, following the earlier practice of Cook and Richards for copper, hardness measurements were used in an extensive investigation of recrystallization. No anomalous behavior was observed as a result of this practice. Specimens which showed complete softening always showed, (metallographically and by X-rays), completely re-crystallized structures. These observations do not, of course, detract in the least from the results of the work under discus-

Jan 1, 1962

By R. E. Ford, P. Tarassoff, P. H. Jennings

Copper oxide ore may be leached at all sizes from run-of-mine down to pulp, and consideration must be given to all available methods in determining the most economical one. Heap leaching was evaluated in a pilot plant at Gaspe Copper Mines, Ltd. which was designed to simultaneously leach two 1200-ton dumps of ore. The plant was operated for two years, in part under severe winter conditions. Two modes of leaching were investigated: acid leaching in which sulfuric acid was added externally to the leach solution, and pyritic leaching in which pyrite concentrate was added to the dump and acid was generated in situ by bacterial action. The pilot plant operation is described, and the results are compared with laboratory data obtained in 6-in.-diam columns. It is concluded that pyritic leaching offers certain operating advantages over acid leaching when copper is recovered by cementation in that iron buildup in the solution is prevented.

Jan 1, 1974

By P. Hajiani

"It has been shown that the economics of the hydrometallurgy of a rare earth process depend upon the amount of acid needed to extract the metal per unit mass of the ore. In this paper, we show how to save a significant amount of acid treating a low grade ferrocarbonatite and extracting +99% constituent REEs. In order to save the acid, the alkali earth metals, originated from gangue minerals were removed prior to REE leaching. Moreover, the operating conditions of leaching reactor are optimized to leave iron behind and to leach REE selectively and effectively. Consequently, the hydrochloric acid consumption per ton of ore drops significantly compared to other processes.INTRODUCTIONThe viability of an extractive metallurgy process of rare earth elements (REEs) to produce an intermediate mixed concentrate depends upon a low-cost simple flowsheet (Bogner, 2014). It has been known that regardless of the mineral, the acid consumption is intimately associated with the operational cost (OPEX) of any REE project, particularly when the initial REE grade is low. Besides acid, the other reagents consumed in the process impact the OPEX. This makes minimizing acid consumption in an REE method a critical priority. The acid consumption in different projects has been reported to be equivalent of 100 kg to 1000 kg HCl (100%) per tonne of ore (Average: 500 kg/t HCl 100%) (Bogner, 2014). This value is strongly correlated with the grade of REE in the ore and therefore in the pre-concentrate.Previously, it has been stated that the Montviel flotation concentrate requires about 300 kg HCl (100%)/t ore to attain +99% REE recoveries using direct leaching (Yu, Verbaan, Pearse and Britt 2013). Hence, for an ore feed rate of 2500 t/d ROM, a large acid production plant (744 t/d HCl 100%) would be required for acid leaching of such concentrate. The equivalent Chlor-alkali plant is estimated to cost M$ 150 (CAPEX) and may require 100 MW power. Therefore, there is a necessity to improve the extractive hydrometallurgy and to reduce the acid consumption significantly."

Jan 1, 2016

By W. R. Dodge

THE growth and development of the assay department of the Hollinger Consolidated Gold Mines, Limited, is a similar story to that of the mine itself. As the mine developed and enlarged, so also increased the demands upon this department, necessitating an increase of capacity for fire assaying and a widening of the scope of work to include chemical analysis, metallurgical tests, research, and screen analysis. The yearly total of determinations, taking an average for the past six years, is approximately 350,000. The major portion of this figure represents fire assaying for gold and silver, being approximately 950 fire assays per day. The assay department occupies the ground floor of the administration building and covers approximately 4,000 square feet of floor space. Ready access is had by motor truck and electric railway for the delivery of samples and the removal of crushed rock and rubbish. The combined weight of all sample rejects amounts to about 5,000 lb. per day, which is sent to the mill bins. There are six departments, each occupying a separate room-grinder room, fluxing room, furnace room, parting room, weighing room, and flux-mixing and storage room.

Jan 1, 1931

By David Segura

THE Huitzuco mercury deposits have been described by C. W. Vaupell,1 therefore the general information such as location, history, production, etc. will not be repeated here. The present owners acquired the property when the deep levels of the Cruz mine were flooded, and it was believed that a relatively large tonnage of low-grade ore and fills would be encountered in the flooded section, because of the early mining methods used in the Cruz mine. The mine was partly unwatered and about 187,000 tons of fills was pit-sampled in the San Cayetano stope. These fills average 2.4 kg. Hg per ton. During the period of maximum production at Huitzuco, the ores were sorted in the mine and cobbed into 3-in. pieces, which were treated in Scott furnaces. Large pieces of raw ore are found in the sinter, and it is indicated that both recovery and costs were not very satisfactory. Recent practice has been to treat the ores in closed retorts made of 10-in. pipes. Because of the presence of combined antimony in the mineral livingstonite (HgS.2Sb2S3) and considerable native sulphur, little or no metallic mercury is recovered in the condensers and a second retorting of the condenser muds is necessary. This makes the treatment of the ores expensive and tends to low recoveries of mercury. The principal costs of retorting are, in their relative order: (1) fuel, (2) low recovery of mercury, (3) replacement of retort pipes, (4) labor. METHODS TESTED Three series of experiments have been made, with the object of reducing the costs of recovering mercury and antimony from the ores, by: (1) wet metallurgical methods, (2) bulk roasting in large mechanical furnaces, (3) concentration to reduce the bulk to be followed by roasting in some mechanical furnace. The wet metallurgical methods did not appear feasible because of the high cost of the alkaline solvents used, and investigations of these were not carried beyond the preliminary stage.

Jan 1, 1938

By Stitt P. H

In Australia, the term "heavy mineral deposits" is used to denote sands which contain variable but economic quantities of the minerals rutile, ilmenite and zircon, often with minor amounts of monazite and xenotime as co-products. Australia has been a significant producer of rutile, ilmenite and zircon from such sands for fifty years and has long been the leading producer of rutile and zircon. The industry had its beginnings with the mining of present day beaches in northern NSW in 1934. Early work was small scale and in some cases involved hand winning of naturally concen- trated mineral for direct export. During World War II and immediately after the industry became increasingly mechanised and by the 1970s on the east coast operated between Newcastle, NSW north to Fraser Island in Queensland. Deposits worked included present day beaches, fossil strand lines up to 5 km or more inland from the present coast and aeolian concentrations. In the mid 1950s, operations commenced on the west coast of WA, south of Perth. Western Australian mineral sands tend to be rich in ilmenite as compared to the east coast. However the WA ilmenites are lower in chrome oxide and make a better syn- thetic rutile feedstock.

Jan 1, 1988

By Carrie Smith

This fall, the Society for Mining, Metallurgy & Exploration (SME) will begin a new chapter by welcoming its new executive director and chief executive officer (CEO). Melissa Russell, a successful nonprofit executive with more than 30 years of experience in global association management, officially stepped into the role on Sept. 29, 2025. She succeeds longtime CEO Dave Kanagy, CAE, who is retiring in March 2026 after more than two decades of transformative leadership. “I am honored to begin this new chapter with SME and inspired by the vital role this community plays in shaping our world,” said Russell. “I look forward to listening, learning and working alongside this remarkable group of professionals to advance innovation, champion sustainability and create a brilliant future together.” Russell brings a deep portfolio of leadership experience in technical and industrial associations to SME. Most recently, she served as executive director of the Institute of Electrical and Electronics Engineers (IEEE) Computer Society, the largest of the IEEE’s 39 societies, with more than 50,000 members across 150 countries. During her tenure, she strengthened global engagement, advanced financial sustainability and launched strategic humanitarian initiatives.

Oct 1, 2025

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887

Jan 1, 1923

By Bernard MacDonald

Introduction. OF the treatment of the slime-pulp of gold- and silver-ores by cyanidation, agitation is an essential part. When prepared for treatment, this pulp, consisting of ore reduced to such fineness that approximately 80 per cent. of it will pass through a 200-mesh screen, is mixed with a certain proportion of water, carrying in solution the quantity of cyanide (KCN) and other chemicals required. The water-constituent of the pulp thus prepared usually ranges from 1 to 2 parts by weight to 1 of the dry ore. Thus constituted', the pulp is charged into treatment-tanks, the shape and capacity of which vary, according to the quantity of pulp to be treated daily and the method of agitation to be employed. Tanks have no other function in a cyanide-plant than that of being economical and convenient containers or receptacles for holding the pulp, solution, or water used in the operations. It is by agitation that the solids in the pulp charged into the tanks are kept in suspension in, and mixed with, the solution in the proper proportions required for the treatment. If the proper mixture of solution to solids be determined to be 2 to 1 by weight (which is, approximately, 5 to 1 by volume), this proportion should be maintained in every part of the charge ; -that is, each solid particle of the pulp, whether it be of 180- or 400-mesh size, should, be surrounded by five times its own volume of solution throughout the whole period of treatment. The reason is, that the amount of chemicals ascertained to be necessary for dissolving the gold and silver contained in the solids, is held in uniform solution in the water-constituent of the pulp, and, therefore, the determined proportions of solution and solids must be maintained at all times during treat-

Apr 1, 1912

By C. K. Leith

GENERAL GEOLOGY OF THE LAKE SUPERIOR IRON-BEARING AND COPPER-BEARING SERIES. THE geology of the Lake Superior region is of general interest, both from an economic and a scientific standpoint. The presence of large and rich iron- and copper-deposits has made a knowledge of the geology of the region necessary for purposes of exploitation and exploration. The ores of the region are contained in rocks of pre-Cambrian age, 'pith for most of the country up to recent years have usually been referred to as « crystalline schists " or " crystalline complex;" and regarded principally as metamorphosed basement-unit upon which the sedimentary rocks, beginning with the Paleozoic, were laid down. In the Lake Superior re¬gion this pre-Cambrian complex presents an unusual variety of rocks with determinable relations. It has been possible, with the large expenditures which-the magnitude of the iron-mining industry warrants, to work out their stratigraphy to a larger extent than has been possible in almost any other area of pre-Cambrian rocks. The real complexity of Lake Superior geology, the confusion of names and the multiplicity of reports covering small parts of the region, are such that interested persons, other than. geologists directly engaged in the work, may well hesitate to attempt to comprehend the geology of the region as a whole. The following paper is a somewhat elementary outline of the geology of the Lake Superior region with special reference to new developments not yet covered in published reports. Geological information concerning the region has been gath¬ered by mining companies, and by the geological surveys of Michigan, Wisconsin, Minnesota, Ontario, Canada, and the United States.. Perhaps in no other part of the country have the mining men themselves spent such large sums in purely geological work. This has made possible the publication of ,reports and maps by the State and Government surveys in much less time and at far less cost than would have been otherwise possible. The. U. S. Geological Survey is the only organization which has covered all of the region on the United 'States side of the boundary, and as its reports include the in¬formation gathered by the mining companies and State organi

Mar 1, 1905

By Jim Galvin

4 and 6 point timber chock constructions are used extensively on both a systematic and spot basis by Australian longwall operators to support tailgate roadways. In 1996, the School of Mining Engineering at UNSW published design and performance criteria for timber chocks constructed from Australian hardwoods. The research was funded by the Australian Coal Association Research Program (ACARP). In 1997, ACARP awarded funding for a stage 2 testing program. This testing focussed on examining the effect of using thinner timber elements in chock constructions to improve OH&S and comparing the full-scale performance of traditional 4 point chocks to Link-n-Lock constructions. It was established that chocks constructed from thinner elements have failure loads much less than thicker elements. However up to the failure loads of the thinner elements there was no significant difference in the response to convergence of chocks constructed from 25, 50 or 100mm thick elements. Chocks constructed from 150mm thick elements have a similar ultimate strength to the 100mm thick elements. However, they have a significantly lower resistance to load, thereby permitting more convergence to occur. There is more potential for chocks comprised of thin elements to be constructed 'out of plumb' and so suffer eccentric loading. The full scale testing program established that at any given level of convergence up to 10% strain, the timber in a Link-n-Lock chock generates twice the support resistance of the same quantity of the same timber in an equivalent size 4 pointer chock. On the basis of support resistance per cubic metre of timber, there is only a marginal difference in the performance of 1.0m Link-n-Lock chocks and 1.2m Link-n-Lock chocks constructed from select Blue Gum. The cost per tonne of support provided by a Link-n-Lock chock is effectively half of that provided by a 4 pointer chock of equivalent dimension and timber. Up to a strain level of 4%. Link-n-Lock chocks constructed from 1.2m long elements are slightly more cost effective than the same chocks constructed from 1.0m long elements. Thereafter, there is no significant difference in cost per tonne of support resistance. Beyond a strain level of about 4%, Link-n¬Lock chocks constructed from landscape grade Blue Gum are just as cost effective as Link-n-Lock chocks constructed from structural grade 4 Blue Gum.

Jan 1, 2000

By O. R. Morris, G. L. Hawkes

A galvanic cell, using as electrolyte a fused salt solution of calcium carbide and as electrodes carbon and a Fe-C alloy of known composition, has been set up to study the thermodynamics of Fe-C alloys in the temperature rmzge 800" to 1000°C. Time independence and reproducibility of the cell electromotive force were taken as evidence of the reversible behavior of the cell. Carbon was believed to be present in the electrolyte as the so-called acetylide ion, C;-. The plots of the cell electromotive force us temperature for a specific alloy composition were straight lines within the limits of experimental error. The average Partial molar enthalpy of carbon in iron relative to pure carbon was found to be +10,610 i 93 cal per g-atom C. Thermodynamic analysis of the data has led to the following equation for the carbon activity, ac, based upon pure carbon as the standard state: In ac = In Zc + 10,560/RT + (10.02 + 77O/T)ZC - 2.350 where ZC is the lattice ratio [nC/(nF, - nc )] and T is the absolute temperature. This equalion gives carbon activity values generally slightly lower than those from gas equilibration studies reported in the literature. METAL LOGRAPHIC examination of a polished cross section of the steel anode used in the electrolysis studies of fused salt solutions of calcium carbide by Morris and Harry revealed extensive carburization of the steel by the electrodeposited carbon. This carburization was reflected in the variability, with time, of the applied potential to the electrolysis cell, necessary to maintain a constant current density at the electrodes. This observation suggested the setting up of a galvanic cell of the "alloy concentration" type to study the thermodynamics of some metal-carbon alloys. Cells of this general type have been widely used for the study of alloy systems.2 In view of the availability of published data in respect of the austenite phase of the Fe-C system, it was decided to carry out measurements upon these alloys before proceeding to studies of less well documented systems. The galvanic cell may be written: where [C] is carbon dissolved in iron. The electrolyte was a fused salt solution of calcium carbide, containing some 5 to 10 mol pct of carbide. The cell reaction is believed to be: C(s)-[CI [I1 Carbon forms an interstitial solid solution in iron, with the atoms located in the octahedral interstices. In the fcc crystal structure of austenite there is one octahedral interstice per iron atom. Thus, the lattice ratio, ZC, shown by Gurney3 to be the fundamental concentration parameter in the context of interstitial solutions, is given by: where nc and nFe are the number of carbon and iron atoms, respectively. chipman4 has recently shown empirically the advantages of using this concentration parameter instead of the more usual atom ratio or atom fraction. The cell electromotive force, E, assuming reversible behavior, is related to the carbon potential or the partial molar free energy of carbon in the solid solution relative to pure carbon at the same temperature and pressure, GP at the composition ZC, by the equation: where z is the carbide ion valency and F is the Faraday constant. An activity of carbon, ac, in the solution relative to the value of unity assigned to pure carbon, and an activity coefficient, qC , are defined such that: where R is the gas constant and T the absolute temperature. GF is further related to the relative partial molar enthalpy Hm, and the temperature coefficient of the cell electromotive force, (aE/aT)Zc, by the equations: Measurement of the cell electromotive force thus enables calculation of the relative partial molar thermodynamic properties of carbon in iron, if z is known. At E = 0, the solid solution is in equilibrium with pure carbon. More convenient for many purposes is the standard state based upon the infinitely dilute solution, Henry's law. The relationship between the activity coefficient of carbon based upon this standard state, and that based upon the pure carbon standard state, qC , may be obtained by considering the free energy of transfer of carbon from the latter standard state to the former. The relationship is: where +:H is the activity coefficient of carbon in the hypothetical standard state based on a reference of

Jan 1, 1969